Emergent Research Trends on the Structural Relaxation Dynamics of Molecular Clusters: From Structure-Property Relationship to New Function Prediction.

ConspectusMolecular clusters (MCs) are monodispersed, precisely defined ensembles of atom collections featured with shape-persistent architectures that can deliver certain functions independently. Their molecular compositions and surface functionalities can be tailored feasibly in a predefined manner, and they can be applied as basic structural units to be engineered into materials with desirable hierarchical structures and enriched functions. The chemical systems also offer great opportunities for the design and fabrication of soft structural materials without the chain topologies of polymers. The bulks of MC assemblies demonstrate viscoelasticity that is used to be considered as the unique feature of polymers, while the MC systems are distinct from polymers since their elasticities are resilient even at temperatures 100 K above their glass transition temperatures. The understanding of their anomalous viscoelasticity and the extended studies of general structure-property relationships are desired for the development of new chemical systems for emergent functions and the possibilities to resolve the intrinsic trade-offs of traditional materials.Meanwhile, general macroscopic functions or properties of materials are related to the transportation of mass, momentum, and/or energy, and they are basically realized or directed by the motions of structural units at different length scales. Structural relaxation dynamics research is critical in quantifying motions ranging from fast bond deformation, bond break/formation, and diffusion of ions and particles to the cooperative motions of structure units. Due to the advancement of measurement technology for relaxation dynamics (e.g., quasi-elastic scattering and broadband dielectric spectroscopy), the structural relaxation dynamics of MC materials have been probed for the first time, and their multiple relaxation modes across several temporal scales were systematically studied to bridge the correlation between molecular structures and macroscopic functions. The fingerprint information from dynamics studies, e.g., the temperature dependence of relaxation time and certain property, e.g., ion conductivity, was proposed to quantify the structure-property relationship, and the microscopic mechanism on the mechanical properties, ion conduction, and gas absorption and separation of MC materials can be fully understood.In this Account, to elucidate the uniqueness of MC materials, especially in comparison with polymers, four topics are mainly summarized: structural features, relaxation dynamics characterization techniques, relaxation dynamics characteristics, and quantified understanding of the structure-property relationship. The capability for new function prediction from relaxation dynamics studies is also introduced, and the typical example in impact resistant materials is provided. The Account aims to prove the significance of relaxation dynamics characterization for material innovation, while it also confirms the potential of MCs for functional material fabrications.

Bioinspired Bouligand-Structured Cellulose Nanocrystals/Poly(vinyl alcohol) Composite Hydrogel for Enhanced Impact Resistance.

Impact-protective materials are gaining importance because of the widespread occurrence of impact damage. Hydrogels have emerged as promising candidates owing to their lightweight and flexible nature. However, achieving soft impact-resistant hydrogels with exceptional stiffness, strength, and toughness remains a challenge. Inspired by the Bouligand structure found in the smasher dactyl club of stomatopods, we propose a straightforward multiscale hierarchical structural design strategy. This strategy integrates self-assembly and salting-out techniques to enhance the impact resistance of soft hydrogels. Rigid cellulose nanocrystals (CNCs) self-assemble into Bouligand-like structures within soft poly(vinyl alcohol) (PVA) matrix via supramolecular interactions. This rational structural design combines the CNC Bouligand structure with a cross-linked network of soft PVA crystalline domains, resulting in a composite hydrogel with impressive mechanical properties: high tensile fracture strength (30.2 MPa), elastic modulus (62.7 MPa), and fracture energy (75.6 kJ m-2), surpassing those of other tough hydrogels. Moreover, the multiscale hierarchical structure facilitates various energy dissipation mechanisms, including crack twisting, tortuous crack paths, and PVA chain orientation, resulting in notable force attenuation (80.4%) in the composite hydrogel. This biomimetic design strategy opens new avenues for developing soft and lightweight impact-resistant materials.

The coupling of rotational and translational dynamics for rapid diffusion of nanorods in macromolecular networks.

The rod-like viruses show anomalously rapid diffusion in bio-tissue networks originated from the rotation-facilitated transportation; however, the experimental investigation of the correlation of the rotational and translational dynamics is still in blank. Herein, typical rod-like and spherical gold nanoparticles (NPs) are dispersed in the classical Tetra-PEG gels, respectively, as model systems for light scattering studies. The contributions from translational and rotational diffusive dynamics, and network fluctuation dynamics can be well-resolved and the stretch exponent of rotational dynamics at 0.25 is proven to be the fingerprint for the coupled rotational and translational dynamics of nanorods. The rotation facilitated re-orientation finally leads to the fast transportation of nanorods. The discoveries are confirmed to be valid for rod-like biomacromolecule systems by studying the diffusive dynamics of Tobacco mosaic virus in gels. The work can be inspiring for the development of protocols to prevent infection of microorganism and regulate the transportation of nano-medicines.

Hierarchical Supramolecular Aggregation of Molecular Nanoparticles for Granular Materials with Ultra High-Speed Impact-Resistance.

The high-speed impact-resistanct materials are of great significance while their development is hindered by the intrinsic tradeoff between mechanical strength and energy dissipation capability. Herein, the new chemical system of molecular granular material (MGM) is developed for the design of impact-resistant materials from the supramolecular complexation of sub-nm molecular clusters (MCs) and hyper-branched polyelectrolytes. Their hierarchical aggregation provides the origin of the decoupling of mechanical strengths and structural relaxation dynamics. The MCs' intrinsic fast dynamics afford excellent high-speed impact-resistance, up to 5600 s-1 impact in a typical split-Hopkinson pressure bar test while only tiny boundary cracks can be observed even under 7200 s-1 impact. The high loadings of MCs and their hierarchical aggregates provide high-density sacrificial bonding for the effective dissipation of the impact energy, enabling the protection of fragile devices from the direct impact of over 200 m s-1 bullet. Moreover, the MGMs can be conveniently processed into protective coatings or films with promising recyclability due to the supramolecular interaction feature. The research not only reveals the unique relaxation dynamics and mechanical properties of MGMs in comparison with polymers and colloids, but also develops new chemical systems for the fabrication of high-speed impact-resistant materials.

The Hybridization of Polymers with Metal Oxide Clusters for the Design of Non-Fluorinated Proton Exchange Membranes.

As the key component of various energy storage and conversion devices, proton exchange membranes (PEMs) have been attracting significant interest. However, their further development is limited by the high cost of perfluorosulfonic acid polymers and the poor stability of acid-dopped non-fluorinated polymers. Recently, a new group of PEMs has been developed by hybridizing polyoxometalates (POMs), a group of super acidic sub-nanoscale metal oxide clusters, with polymers. POMs can serve simultaneously as both proton sponges and stabilizing agents, and their complexation with polymers can further improve polymers' mechanical performance and processability. Enormous efforts have been focused on studying supramolecular complexation or covalent grafting of POMs with various polymers to optimize PEMs in terms of cost, mechanical properties and stabilities. This concept summarizes recent advances in this emerging field and outlines the design strategies and application perspectives employed for using POM-polymer hybrid materials as PEMs.

Supramolecular Complexation Reinforced Polymer Frustrated Packing: Controllable Dual Porosity for Improved Permselectivity of Coordination Nanocage Mixed Matrix Membranes.

The developments of mixed matrix membranes (MMMs) are severely hindered by the complex inter-phase interaction and the resulting poor utilization of inorganics' microporosity. Herein, a dual porosity framework is constructed in MMMs to enhance the accessibility of inorganics' microporosity to external gas molecules for the effective application of microporosity for gas separation. Nanocomposite organogels are first prepared from the supramolecular complexation of rigid polymers and 2 nm microporous coordination nanocages (CNCs). The network structures can be maintained with microporous features after solvent removal originated from the rigid nature of polymers, and the strong coordination and hydrogen bond between the two components. Moreover, the strong supramolecular attraction reinforces the frustrated packing of the rigid polymers on CNC surface, leading to polymer networks' extrinsic pores and the interconnection of CNCs' micro-cavities for the fast gas transportation. The gas permeabilities of the MMMs are 869 times for H2 and 1099 times for CO2 higher than those of pure polymers. The open metal sites from nanocage also contribute to the enhanced gas selectivity and the overall performance surpasses 2008 H2/CO2 Robeson upper bound. The supramolecular complexation reinforced packing frustration strategy offers a simple and practical solution to achieve improved gas permselectivity in MMMs.

Retrospective Analysis of Structure-Property Relationship of Emergent Metallo-Supramolecular Polymer Networks.

Metallo-supramolecular polymer networks (MSPNs) are fabricated from the crosslinking of polymers by discrete supramolecular coordination complexes. Due to the availability of various coordination complexes, e. g., 2D macrocycles and 3D nanocages, the MSPNs have been recently developed with broadly tunable visco-elasticity and enriched functions inherited from the coordination complexes. The coordination complexes possess enriched topologies and unique structural relaxation dynamics, rendering them the capability to break the traditional tradeoffs of polymer systems for the design of materials with enhanced mechanical performance. The structure-property relationship studies are critical for the material-by-design of MSPNs, while the spatiotemporal investigations are desired for the exploration of dynamics information. The work summarizes recent studies on the unique ligand-exchange kinetics and the multi-level structural relaxation dynamics of MSPNs. The MSPNs' mechanical properties can be quantitatively correlated with the dynamics for understanding the structure-property relationship. This concept will not only serve to attract more researchers to engage in the study of the structure-activity relationship of MSPNs but also inspire innovative research findings pertaining to the application of MSPNs.

Exploration of Molecular Nanoparticles as Soft Structural Materials and Their Structure-Property Relationship.

The search for alternative chemical systems other than polymers with chain topologies for soft structural materials raises general interests in fundamental materials and chemical sciences. It is also appealing from an engineering perspective for the urgent need to resolve the typical trade-offs of polymer systems. Herein, a subnanometer molecular cluster, polyhedral oligomeric silsesquioxanes, is assembled into molecular nanoparticles (MNPs) with star topology. Broadly tunable viscoelasticity can be realized by fine-tuning the MNPs' deformability. Being analogous to polymeric systems, the hierarchical structural relaxation dynamics can be observed, and their relaxation time and temperature dependence are dominated by the linker flexibilities. This not only provides microscopic understanding on MNP's unique viscoelasticity but also offers enormous opportunities for modulating their mechanical properties via linker engineering. Our work proves the possibility of applying structural units with particle topologies for the design of soft structural materials.

Particle topology-regulated relaxation dynamics in cluster-ordering.

The granular materials of soft particles (SPs) demonstrate unique viscoelasticity distinct from general colloidal and polymer systems. Exploiting dynamic light scattering measurements, together with molecular dynamics simulations, we study the diffusive dynamics of soft particle clusters (SPCs) with spherical and cylindrical brush topologies, respectively, in the melts of SPs. A topologically constrained relaxation theory is proposed by quantitatively correlating the relaxation time to the topologies of the SPCs, through the mean free space (Va) of tethered SPs in the cluster. The tethered SPs in SPCs are crowded by SPs of the melts to form the cage zones, and the cooperative diffusion of the tether SPs in the zones is required for the diffusive motion of SPCs. The cage zone serves as an entropic barrier for the diffusion of SP clusters, while its strength is determined by Va. Three characteristic modes can be confirmed: localized non-diffusive mode around critical Va, diffusive mode with Va deviating far from the critical value, and a sub-diffusive mode as an interlude between two limits. Our studies raise attention to the emergent physical properties of materials based on SPs via a topological design while opening new avenues for the design of soft structural materials.

Photoresponsive Viscoelasticity of the Granular Materials of Azobenzene-Bearing Molecular Nanoparticles.

The large sizes of granular particles lead to their slow diffusive dynamics and significant interparticle friction, bringing enormous difficulty to tune the mechanical properties and processability of the granular materials (GMs). Herein, 1 nm polyhedral oligomeric silsesquioxane (POSS) particles functionalized with azobenzene are designed as structural units, and the obtained GMs show unique photoswitchable viscoelasticity. The azobenzene group can undergo a reversible trans-cis conformation switch while the π-π stacking among the azobenzene fragments is only favored by the trans-conformation due to molecular geometrical requirements. The POSS units from neighboring assemblies close pack to form microdomains, and the POSS is under confinement by both the supramolecular bonding and the other POSS in the microdomains. The simultaneous breaking of the two types of confinement is difficult and, therefore, the free diffusion of POSS is hindered, leading to the elasticity of the GMs of trans-POSS. For cis-POSS, the interparticle supramolecular interaction is weak and the POSS unit can undergo free diffusion, contributing to their high flowability at room temperature. The photoswitching viscoelasticity of GMs is further used for self-healing and photoswitchable adhesion. This work paves new pathways for the regulation of material viscoelasticity and the design of GM-based smart materials.

Unique Viscoelasticity and Hierarchical Relaxation Dynamics of Molecular Granular Materials.

Resulting from the dense packing of subnanometer molecular clusters, molecular granular materials (MGMs) are shown to maintain high elasticity far above their apparent glass transition temperature (Tg*). However, our microscopic understanding of their structure-property relationship is still poor. Herein, 1 nm polyhedral oligomeric silsesquioxanes (POSSs) are appended to a backbone chain in a brush configuration with different flexible linker chains. Assemblies of these brush polymers exhibit hierarchical relaxation dynamics with the glass transition arising from the cooperative dynamics of packed POSSs. The interaction among the assemblies can be strengthened by increasing the rigidity of linkers with the MGM relaxation modes changing from colloid- to polymer chain-like behavior, rendering their tunable viscoelasticity. This finally contributes to the decoupling of mechanical and thermal properties by showing elasticity dominant mechanical properties at a temperature 150 K above the Tg*.

Supramolecular Complexation of Metal Oxide Cluster and Non-Fluorinated Polymer for Large-Scale Fabrication of Proton Exchange Membranes for High-Power-Density Fuel Cells.

Cost-effective, non-fluorinated polymer proton exchange membranes (PEMs) are highly desirable in emerging hydrogen fuel cells (FCs) technology; however, their low proton conductivities and poor chemical and dimension stabilities hinder their further development as alternatives to commercial Nafion®. Here, we report the inorganic-organic hybridization strategy by facilely complexing commercial polymers, polyvinyl butyral (PVB), with inorganic molecular nanoparticles, H3 PW12 O40 (PW) via supramolecular interaction. The strong affinity among them endows the obtained nanocomposites amphiphilicity and further lead to phase separation for bi-continuous structures with both inter-connected proton transportation channels and robust polymer scaffold, enabling high proton conductivities, mechanical/dimension stability and barrier performance, and the H2 /O2 FCs equipped with the composite PEM show promising power densities and long-term stability. Interestingly, the hybrid PEM can be fabricated continuously in large scale at challenging ~10 µm thickness via typical tape casting technique originated from their facile complexing strategy and the hybrids' excellent mechanical properties. This work not only provides potential material systems for commercial PEMs, but also raises interest for the research on hybrid composites for PEMs.

Controllable and Reversible Assembly of Nanofiber from Natural Macromolecules via Protonation and Deprotonation.

Nanofiber is the critical building block for many biological systems to perform various functions. Artificial assembly of molecules into nanofibers in a controllable and reversible manner will create "smart" functions to mimic those of their natural analogues and fabricate new functional materials, but remains an open challenge especially for nature macromolecules. Herein, the controllable and reversible assembly of nanofiber (CSNF) from natural macromolecules with oppositely charged groups are successfully realized by protonation and deprotonation of charged groups. By controlling the electrostatic interaction via protonation and deprotonation, the size and morphology of the assembled nanostructures can be precisely controlled. A strong electrostatic interaction contributes to large nanofiber with high strength, while poor electrostatic interaction produces finer nanofiber or nanoparticle. And especially, the assembly, disassembly, and reassembly of the nanofiber occurs reversibly through protonation and deprotonation, thereby paving a new way for precisely controlling the assembly process and structure of nanofiber. The reversible assembly allows the nanostructure to dynamically reorganize in response to subtle perturbation of environment. The as-prepared CSNF is mechanical strong and can be used as a nano building block to fabricate high-strength film, wire, and straw. This study offers many opportunities for the biomimetic synthesis of new functional materials.

Spatiotemporal Studies of Soluble Inorganic Nanostructures with X-rays and Neutrons.

This Review addresses the use of X-ray and neutron scattering as well as X-ray absorption to describe how inorganic nanostructured materials assemble, evolve, and function in solution. We first provide an overview of techniques and instrumentation (both large user facilities and benchtop). We review recent studies of soluble inorganic nanostructure assembly, covering the disciplines of materials synthesis, processes in nature, nuclear materials, and the widely applicable fundamental processes of hydrophobic interactions and ion pairing. Reviewed studies cover size regimes and length scales ranging from sub-Ångström (coordination chemistry and ion pairing) to several nanometers (molecular clusters, i.e. polyoxometalates, polyoxocations, and metal-organic polyhedra), to the mesoscale (supramolecular assembly processes). Reviewed studies predominantly exploit 1) SAXS/WAXS/SANS (small- and wide-angle X-ray or neutron scattering), 2) PDF (pair-distribution function analysis of X-ray total scattering), and 3) XANES and EXAFS (X-ray absorption near-edge structure and extended X-ray absorption fine structure, respectively). While the scattering techniques provide structural information, X-ray absorption yields the oxidation state in addition to the local coordination. Our goal for this Review is to provide information and inspiration for the inorganic/materials science communities that may benefit from elucidating the role of solution speciation in natural and synthetic processes.

Strain-Induced Heteromorphosis Multi-Cavity Cages: Tension-Driven Self-Expansion Strategy for Controllable Enhancement of Complexity in Supramolecular Assembly.

Coordinative supramolecular cages with adjustable cavities have found extensive applications in various fields, but the cavity modification strategies for multi-functional structures are still challenging. Here, we present a tension-driven self-expansion strategy for construction of multi-cavity cages with high structural complexity. Under the regulation of strain-induced capping ligands, unprecedented heteromorphosis triple-cavity cages S2 /S4 were obtained based on a metallo-organic ligand (MOL) scaffold. The heteromorphosis cages exhibited significant higher cavity diversity than the homomorphous double-cavity cages S1 /S3 ; all of the cages were thoroughly characterized through various analytical techniques including (1D and 2D) NMR, ESI-MS, TWIM-MS, AFM, and SAXS analyses. Furthermore, the encapsulation of porphyrin in the cavities of these multi-cavity cages were investigated. This research opens up new possibilities for the architecture of heteromorphosis supramolecular cages via precisely controlled "scaffold-capping" assembly with preorganized ligands, which could have potential applications in the development of multifunctional structures with higher complexity.

Polyoxometalate-Organic Hybrid "Calixarenes" as Supramolecular Hosts.

Calixarenes are among the most useful and versatile macrocycles in supramolecular chemistry. The one thing that has not changed in the 80 years since their discovery, despite numerous derivatizations, is their fully organic, covalent scaffolds. Here, we report a new type of organic-inorganic hybrid "calixarenes" constructed by means of coordination-driven assembly. Replacing acetate ligands on the {SiW10 Cr2 (OAc)2 } clusters with 5-hydroxyisophthalates allows these 95° inorganic building blocks to be linked into bowl-shaped, hybrid "calix[n]arenes" (n=3, 4). With a large concave cavity, the metal-organic calix[4]arene can accommodate nanometer-sized polyoxoanions in an entropically driven process. The development of hybrid variants of calixarenes is expected to expand the scope of their physicochemical properties, guest/substrate binding, and applications on multiple fronts.

The Coordination Nanocages-Integrated Polymer Brush Networks for Flexible Microporous Membranes with Exceptional H2 /CO2 Separation Performance.

The emergence of polymers with intrinsic microporosity provides solutions for flexible gas separation membranes with both high gas permeability and selectivity. However, their applications are significantly hindered by the costly synthetic efforts, limited availability of chemical systems, and narrow window of microporosity sizes. Herein, flexible mixed matrix membranes with tunable intrinsic microporosity can be facilely fabricated from the coordination assembly of polymer brushes and coordination nanocages. Polymer brushes bearing isophthalic acid side groups can coordinate with Cu2+ to assemble into polymer networks crosslinked by 2 nm nanocages. The semi-flexible feature of the polymer brush and the high crosslinking density of the network prevent the network from collapsing during solvent removal and the obtained aerogels demonstrate hierarchical structure with dual porosity from the crosslinked polymer network and coordination nanocage, respectively. The porosity can be facilely tuned via the amount of Cu2+ by regulating the network crosslinking density and nanocage loadings, and finally, optimized gas separation that surpasses Robeson upper bound for H2 /CO2 can be achieved. The coordination-driven assembly protocol paves a new avenue for the cost-effective synthesis of polymers with intrinsic microporosity and the fabrication of flexible gas separation membranes.

Modulating Ligand-Exchange Dynamics on Metal-Organic Polyhedra for Reversible Sorting and Hybridization of Miktoarm Star Polymers.

The precise synthesis of miktoarm star polymers (MSPs) remains one of the great challenges in synthetic chemistry due to the difficulty in locating appropriate structural templates and polymer grafting/growing strategies with high selectivity and efficiency. Herein, ≈2 nm metal-organic polyhedra (MOPs), constructed from the coordination of isophthalic acid (IPA) and Cu2+ , are applied as templates for the precise synthesis of 24-arm MSPs for their unique logarithmic ligand-exchange dynamics. Six different polymers are prepared with IPA as an end group and they further coordinated with Cu2+ to afford the corresponding 24-arm star homo-polymers. MSPs can be obtained by mixing targeted homo-arm star polymers in solutions upon thermal annealing. The compositions of MSPs can be facilely and precisely tuned by the recipe of the star polymer mixtures used. Interestingly, the obtained MSPs can be sorted into homo-arm star polymers through a typical solvent extraction procedure. The hybridization and sorting process can be reversibly conducted through the cycle of thermal annealing and solvent treatment. The complex coordination framework not only opens new avenues for the facile and precise synthesis of MSPs and MOPs with hybrid functionalities, but also provides the capability to design sustainable polymer systems.

Correlation of Structure and Dynamics Behavior in Polyzwitterions: From Concentrated Solution to Gel-Like State.

The dynamic behaviors of polyzwitterions, poly(4-((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate) (PSBP), are investigated using dynamic light scattering, small angle X-ray scattering, and rheology.  The findings reveal two relaxation modes, including a fast and a slow mode, which  are observed in both solution state and gel-like state, with varying polyzwitterion concentration (CP ) and NaCl concentration (CNaCl ). As CP and CNaCl increasing, a slower slow mode and a faster fast mode are observed. The fast mode corresponds to the diffusion of chains, while the slow mode arises from chain aggregations. In solutions, the slow mode is dominated by the diffusion of chain aggregations. However, in the gel-like state, the "cage network" traps aggregations more densely, leading to their dynamic behavior being dominated by enhanced topological entanglements and ionic interactions. This difference highlights the unique nature of the slow relaxation mode between concentrated solution and gel-like state, arising from changes in the average distance between chain aggregations resulting from increased CP and CNaCl concentrations.

Molecular Complexation of Polymers and Metal Oxide Clusters for Semicrystalline, Thermoplastic Anhydrous Proton Exchange Membranes in Fuel Cells.

With the manipulation of surface charges and loadings, 1 nm super-acidic metal oxide clusters can co-crystallize with poly(ethylene glycol) (PEG) at molecular scale for thermoplastic anhydrous proton exchange membranes (PEMs). The coexistence of crystalline and amorphous regions endows the PEMs with a high Young's modulus and high flexibility, while the noncovalent complex interactions enable facile preparation and (re)processing. Furthermore, the diffusive dynamics of PEG chains is slowed by the confinement effect, while the local segmental dynamics is accelerated due to the transition of the chain conformation from helix to zigzag when confined in the crystalline framework. This greatly facilitates proton transportation in the crystalline region for an excellent anhydrous proton conductivity of 4.5 × 10-3 S cm-1 at 90 °C. The balanced proton conductivity, mechanical strength, and processability of the PEMs contribute to the promising power density of H2/O2 fuel cells assembled with co-crystalline PEMs at high temperatures under dry conditions.